CN116770133A - Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board - Google Patents
Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board Download PDFInfo
- Publication number
- CN116770133A CN116770133A CN202310724956.5A CN202310724956A CN116770133A CN 116770133 A CN116770133 A CN 116770133A CN 202310724956 A CN202310724956 A CN 202310724956A CN 116770133 A CN116770133 A CN 116770133A
- Authority
- CN
- China
- Prior art keywords
- deformation
- percent
- rolling
- time
- elongation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000011206 ternary composite Substances 0.000 title claims abstract description 29
- 238000005096 rolling process Methods 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000003723 Smelting Methods 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 14
- 238000001192 hot extrusion Methods 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 6
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910008266 Li-Ag Inorganic materials 0.000 claims description 4
- 229910008445 Li—Ag Inorganic materials 0.000 claims description 4
- 229910006309 Li—Mg Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000001550 time effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite plate, in particular to a casting-extrusion-rolling manufacturing technology of Zn-Li-x (x=Mg/Ag/Fe) alloy. The Zn-Li-x ternary composite board comprises the following components in percentage by mass: li 0.4-0.6%; x is 0.05 to 0.15 percent; the balance of zinc; the x is selected from one of Mg, ag and Fe; the preparation method comprises the following steps: smelting and casting the components according to the design components to obtain cast ingots; then homogenizing annealing and extruding to obtain an extruded bar; the bar is rolled by multiple times of deformation change after heat treatment to obtain a composite board with the thickness of 0.1-1 mm; obtaining the finished product. The invention has reasonable component design and simple preparation process, and the obtained product has high strength, high elongation and proper hardness.
Description
Technical Field
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite plate, in particular to a casting-extrusion-rolling manufacturing technology of Zn-Li-x (x=Mg/Ag/Fe) alloy.
Background
With the increasing life span of human beings, the medical science and technology level has also been developed more and more, and more severe requirements have been put on the reliability and life span of medical degradable materials. Therefore, the development of the design and preparation technology of the medical degradable material is always receiving great attention and broad attention internationally. Through years of development, the current medical materials mainly comprise Fe-based alloy, mg-based alloy and Zn-based alloy, and a large number of research works show that the degradation rate of the Zn-based alloy is moderate, so that the Zn-based alloy is degraded at a proper rate in the service process of the medical degradable material. Most of the research efforts at present have focused on the design and simple plastic deformation of material alloy systems. In order to promote the healthy and rapid development of medical degradable materials, research work in the aspects of material system design, biological property evaluation and the like is still a main aspect of attention at present.
The structure of Zn alloys mainly consists of matrix phases (α -Zn) and intermetallic phases, the intermetallic phases and their volume fractions, sizes and distributions in the Zn matrix have a significant influence on the mechanical properties of the Zn alloy, and these microstructure features depend on the preparation method and the processing method. The current research work has certain limitation, the influence of different Li contents on the structure and mechanical properties is researched, the biological characteristics of the alloy under specific Li contents are researched, or the research work is only carried out on an as-cast state or a final rolled state, and the post-processing such as extrusion/rolling and the like are not carried out on Zn-Li binary alloys under different Li contents, and the biological characteristic research is carried out. Moreover, the prior published data do not relate to how to synchronously improve the hardness, the strength and the elongation of the Zn-0.5Li-x ternary composite board.
Disclosure of Invention
The invention provides a method for synchronously improving the hardness, strength and elongation of a product on the basis of earlier study of the subject group (such as CN 108396176A) and on the basis of ensuring the biological characteristics of the product.
The method further improves the hardness of the product through the control of the rolling deformation for the first time, and ensures that other mechanical property indexes are not seriously attenuated.
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; the Zn-Li-x ternary composite board comprises the following components in percentage by mass:
Li 0.4～0.6％；
x 0.05～0.15％；
the balance of zinc; the x is selected from one of Mg, ag and Fe;
the preparation method comprises the following steps:
the method takes as-cast Zn-Li-x ternary alloy as a treatment object and comprises the following steps:
step one homogenizing annealing
Heating the as-cast Zn-Li-x ternary alloy to 250-350 ℃, carrying out homogenizing annealing for 24-60h, and then adopting water quenching to obtain a zinc alloy cast ingot A with uniform structure;
step two extrusion
The zinc alloy cast ingot A is immediately taken out after heat preservation for 50-80 min at 200-400 ℃ and is hot extruded by a die with fixed size in extrusion equipment to obtain bars with the diameter of 10-20mm, and the extrusion ratio in the process is 5:1-20:1;
step three heat treatment
Preserving the temperature of the extruded bar for 0.5-2 hours at 150-300 ℃ to obtain the bar subjected to aging heat treatment;
step four rolling
And (3) carrying out multi-pass rolling on the bar subjected to the aging heat treatment, wherein the deformation of each pass is between 10 and 30 percent, and finally obtaining the composite board with the thickness of 0.1 to 1 mm.
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; the as-cast Zn-Li-x ternary alloy is prepared by the following steps:
(1) Smelting: firstly, putting a high-purity Zn matrix into a smelting crucible, adding high-purity Li metal after Zn is melted, stirring for a period of time after adding to ensure that different components are uniformly distributed, adding a high-purity third element by the same method after stirring for continuous stirring when preparing a ternary alloy, and preheating equipment and raw materials to a certain degree in the smelting process, wherein the preheating is generally carried out at 200-300 ℃; when smelting, the temperature is controlled to be 400-600 DEG C
(2) Casting: the heating device can be turned off after the mixture is uniformly stirred, impurities on the surface of the melt can be removed after the mixture is stable in temperature, the mixture is poured in a die, and the die is removed after the mixture is completely cooled and solidified, so that the cast alloy with the expected size can be obtained.
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; in the first step, the homogenizing annealing temperature is 295-305 ℃ and the homogenizing annealing time is 46-50 h.
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; and step two, taking out the zinc alloy cast ingot A immediately after heat preservation for 60min at 295-305 ℃ and carrying out hot extrusion in extrusion equipment through a die with fixed size to obtain a bar with the diameter of 15-17 mm.
The invention relates to a method for synchronously improving the hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; in the fourth step, the bar after the time-effect heat treatment is rolled for multiple times, the deformation of each pass is between 10 and 30 percent, and the deformation of the first rolling is larger than the deformation of any subsequent rolling; and the deformation amount of the nth rolling is larger than that of the n+1th rolling.
Or (b)
The invention relates to a preparation method of a Zn-Li-x ternary composite board with medical degradability and moderate hardness, which comprises the following steps of carrying out multi-pass rolling on a bar after time-efficient heat treatment, wherein the deformation of each pass is between 10 and 30 percent, and the deformation of the first rolling is smaller than the deformation of any subsequent rolling; and the deformation amount of the nth rolling is smaller than that of the n+1th rolling.
When a Zn-Li-Mg as-cast alloy containing 0.5wt% Li and 0.1 wt% Mg is used,
homogenizing annealing at 300 deg.c for 48 hr, and water quenching at room temperature to obtain homogeneous Zn-0.5-0.1% Mg alloy ingot; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 30 percent, the rolling times are 5 times, the deformation of each time is decreased, and the deformation of the last time is 10 percent to obtain the Zn-0.5 percent Li-0.1 percent Mg composite plate; the hardness, modulus, tensile strength and elongation of the Zn-0.5 percent Li-0.1 percent Mg composite board are respectively 1.01GPa, 142.37GPa, 306.5MPa and 27.9 percent.
When a Zn-Li-Mg cast alloy containing 0.5wt% of Li and 0.1% of Mg is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Mg alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 10 percent, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 30 percent to obtain a Zn-0.5 percent Li-0.1 percent Mg composite plate; the hardness, modulus, bending strength and elongation of the Zn-0.5 percent Li-0.1 percent Mg composite board are respectively 0.98GPa, 136.43GPa, 318.6MPa and 26.8 percent.
When a Zn-Li-Ag cast alloy containing 0.5wt% of Li and 0.1% of Ag is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Ag alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is 30-10%, the deformation of the first time is 30%, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 10%, so as to obtain the Zn-0.5% Li-0.1% Ag composite plate; the hardness, young's modulus, bending strength and elongation of the Zn-0.5% Li-0.1% Ag composite plate are respectively 1.02GPa, 83.17GPa, 251.6MPa and 92.7%.
When a Zn-Li-Ag cast alloy containing 0.5wt% of Li and 0.1% of Ag is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Ag alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 10 percent, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 30 percent to obtain a Zn-0.5 percent Li-0.1 percent Ag composite plate; the hardness, young's modulus, bending strength and elongation of the Zn-0.5% Li-0.1% Ag composite plate are respectively 0.99GPa, 81.36GPa, 254.8MPa and 94.1%.
According to the preparation method of the Zn-Li-x ternary composite plate with the medical degradability and moderate hardness, disclosed by the invention, the cast ingot is extruded into the bar in the extrusion process, so that the stress concentration and the tissue defect generated in the process of extruding the plate can be effectively reduced, and the mechanical property of the material can be obviously improved.
The preparation method of the Zn-Li-x ternary composite board with medical degradability and moderate hardness realizes structural function integration, and is suitable for being used as a promising medical degradable implant material.
By adopting the process designed by the invention, the prepared ternary composite board has higher tissue uniformity and reduces the phenomenon of stress concentration in a material matrix.
The invention can realize mass production of materials and further reduce the production cost.
Advantages and advantages
1. The invention can realize the uniform distribution of elements by controlling the melting process;
2. according to the invention, the bar is obtained through optimization of the extrusion process, so that stress concentration and tissue defects generated by uneven stress in the extrusion process can be reduced;
3. the preparation method has the advantages of simple process and low cost, and can realize batch production of materials and further reduce the production cost;
4. the hardness of the product is moderate; and compared with the cast state, the mechanical property of the product is obviously improved.
Drawings
FIG. 1 is a schematic diagram of a preparation route for preparing a medical degradable Zn-Li-x (x=Mg/Ag/Fe) ternary composite board in the invention.
FIG. 2 shows the microstructure and grain size distribution results of Zn-0.5% Li-0.1% Mg composite sheet material prepared in example 1.
FIG. 3 shows the microstructure and grain size distribution results of Zn-0.5% Li-0.1% Ag composite sheet prepared in example 4.
Fig. 4 is a xRD spectrum of the three medical degradable alloys obtained in example 1, example 4 and comparative example, and it can be seen that the generated secondary phase cannot be represented in xRD spectrum due to the too small content of the added third component.
Fig. 5 is electrochemical corrosion curves of three medical degradable alloys obtained in example 1, example 4 and comparative example, and it can be seen that the addition of the third component has a significant effect on the degradation rate of the control alloy.
Detailed Description
The preparation technology of the medical degradable Zn-Li-x (x=Mg/Ag/Fe) ternary composite board is further described below with reference to the accompanying drawings and the specific embodiments.
Example 1
(1) Smelting: firstly, putting 99.4% of Zn blocks with the purity of 99.9% into a smelting crucible, uniformly stirring after Zn is melted, adding 0.5% of Li particles with the purity of 99.9%, continuously uniformly stirring, adding 0.1% of Mg blocks with the purity of 99.9%, and carrying out certain preheating on equipment and raw materials in the smelting process, wherein the preheating is carried out at 200 ℃; the smelting temperature is 550 ℃;
(2) Casting: after the mixture is stirred uniformly, the heating device can be turned off, impurities on the surface of the melt can be removed after the temperature is stabilized at 500 ℃, the melt is poured in a mould, and after the melt is completely cooled and solidified, demoulding is carried out, so that the Zn-0.5 percent Li-0.1 percent Mg cast alloy with the expected size can be obtained.
(3) Homogenizing and annealing: in order to eliminate residual stress in the as-cast alloy, carrying out homogenizing annealing for 48 hours at 300 ℃ on the cast ingot before extrusion, and carrying out water quenching at room temperature to obtain a Zn-0.5 percent Li-0.1 percent Mg alloy cast ingot with uniform structure;
(4) Extruding: taking out the cast ingot obtained in the step 3 immediately after heat preservation for 1h at 300 ℃, and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar with the diameter of 16mm, wherein the extrusion ratio in the process is about 10:1;
(5) And (3) heat treatment: carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h;
(6) Rolling: and (3) carrying out multi-pass rolling on the bar in the step (5), wherein the deformation of each pass is 30-10% (the deformation of the bar in the first pass is 30%, the rolling times are 5 times, the deformation of the bar in each pass is reduced, and the deformation of the bar in the last pass is 10%), and finally obtaining the Zn-0.5% Li-0.1% Mg composite plate with the thickness of 1 mm.
The medical degradable Zn-0.5% Li-0.1% Mg composite board obtained in the embodiment is subjected to mechanical property test, and the hardness, young's elastic modulus, tensile strength and elongation are respectively 1.01GPa, 142.37GPa, 306.5MPa and 27.9%. The microstructure and grain size distribution are shown in fig. 2.
Example 2
Other conditions were the same as in example 1, and the deformation per pass in step (6) was fixed at 20%; the hardness, young's modulus, flexural strength and elongation of the obtained product were 1.02GPa, 144.67GPa, 301.7MPa and 24.7%, respectively.
Example 3
Other conditions are consistent with example 1, the deformation of the first pass in the step (6) is 10%, then the deformation is gradually increased, 5 times of rolling are carried out, and the deformation of the last time of rolling is 30%; the hardness, young's modulus, flexural strength and elongation of the obtained product were 0.98GPa, 136.43GPa, 318.6MPa and 26.8%, respectively.
As can be seen from the comparative examples of examples 1 and 3, when the components are identical (namely Zn-0.5% Li-0.1% Mg) and other processes are identical, the deformation of the large deformation amount is firstly carried out, the product with the maximum elongation is obtained by decreasing the deformation amount, and the hardness, the elastic modulus and the strength of the product are all good. When the scheme of small variable subsequent increment is adopted, the hardness, the elastic modulus and the elongation of the obtained product are slightly reduced compared with the former scheme, but the strength is improved.
Comparative example 1
Other conditions were the same as in example 1, except that steps (3) to (6) were omitted, and the hardness, young's modulus, flexural strength and elongation of the obtained product (i.e., as-cast product) were 0.91GPa, 135.42GPa, 173.84MPa and 9.76%, respectively.
Example 4
(1) Smelting: firstly, putting 99.4% of Zn blocks with the purity of 99.9% into a smelting crucible, uniformly stirring after Zn is melted, adding 0.5% of Li particles with the purity of 99.9%, continuously uniformly stirring, adding 0.1% of Ag sheets with the purity of 99.9%, and carrying out certain preheating on equipment and raw materials in the smelting process, wherein the preheating is carried out at 200 ℃; the smelting temperature is 550 ℃;
(2) Casting: after the mixture is stirred uniformly, the heating device can be turned off, impurities on the surface of the melt can be removed after the temperature is stabilized at 500 ℃, the melt is poured in a mould, and after the melt is completely cooled and solidified, the demoulding is carried out, so that the Zn-0.5 percent Li-0.1 percent Ag cast alloy with the expected size can be obtained.
(3) Homogenizing and annealing: in order to eliminate residual stress in the as-cast alloy, carrying out homogenizing annealing for 48 hours at 300 ℃ on the cast ingot before extrusion, and carrying out water quenching at room temperature to obtain a Zn-0.5 percent Li-0.1 percent Ag alloy cast ingot with uniform structure;
(4) Extruding: taking out the cast ingot obtained in the step 3 immediately after heat preservation for 1h at 300 ℃, and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar with the diameter of 16mm, wherein the extrusion ratio in the process is about 10:1;
(5) And (3) heat treatment: carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h;
(6) Rolling: and (3) carrying out multi-pass rolling on the bar in the step (5), wherein the deformation of each pass is between 10 and 30 percent (the deformation of the bar in the first pass is 30 percent, the rolling times are 5 times, the deformation of the bar in each pass is reduced, the deformation of the bar in the last pass is 10 percent), and finally processing to obtain the Zn-0.5 percent Li-0.1 percent Ag composite plate with the thickness of 1 mm.
The medical degradable Zn-0.5% Li-0.1% Ag ternary composite board obtained in the embodiment is subjected to performance test, and the hardness, modulus, tensile strength and elongation are respectively 1.02GPa, 83.17GPa, 251.6MPa and 92.7%. The microstructure and grain size distribution are shown in FIG. 3.
Example 5
Other conditions were consistent with example 4, with the deformation per pass in step (6) fixed at 20%; the hardness, modulus, flexural strength and elongation of the obtained product were 1.04GPa, 88.17GPa, 241.6MPa and 83.2%, respectively.
Example 6
Other conditions are consistent with example 4, the deformation amount of the first pass in the step (6) is 10%, then the deformation amount is gradually increased, 5 times of rolling are carried out, and the deformation amount of the last time of rolling is 30%; the hardness, modulus, flexural strength and elongation of the obtained product were 0.99GPa, 81.36GPa, 254.8MPa and 94.1%, respectively.
As can be seen from the comparative examples of examples 4 and 6, when the components are completely the same (namely Zn-0.5% Li-0.1% Ag), and the other processes are completely the same, the deformation of large deformation is firstly carried out, and the deformation is reduced, so that a product with moderate mechanical properties is obtained. When a scheme of small variable subsequent increment is adopted first, the elongation and strength of the obtained product are improved relative to the previous scheme. Compared with the cast state, the comprehensive performance of the product is obviously improved.
Comparative example 2
Other conditions were the same as in example 4, except that steps (3) to (6) were omitted, and the hardness, modulus, flexural strength and elongation of the obtained product were 0.95GPa, 76.54GPa, 185.83MPa and 16.92%, respectively.
Claims (9)
1. A method for synchronously improving hardness, strength and elongation of a medical degradable Zn-Li-x ternary composite board; the Zn-Li-x ternary composite board comprises the following components in percentage by mass:
Li 0.4～0.6％；
x 0.05～0.15％；
the balance of zinc; the x is selected from one of Mg, ag and Fe;
the preparation method comprises the following steps:
the method takes as-cast Zn-Li-x ternary alloy as a treatment object and comprises the following steps:
step one homogenizing annealing
Heating the as-cast Zn-Li-x ternary alloy to 250-350 ℃, carrying out homogenizing annealing for 24-60h, and then adopting water quenching to obtain a zinc alloy cast ingot A with uniform structure;
step two extrusion
The zinc alloy cast ingot A is immediately taken out after heat preservation for 50-80 min at 200-400 ℃ and is hot extruded by a die with fixed size in extrusion equipment to obtain bars with the diameter of 10-20mm, and the extrusion ratio in the process is 5:1-20:1;
step three heat treatment
Preserving the temperature of the extruded bar for 0.5-2 hours at 150-300 ℃ to obtain the bar subjected to aging heat treatment;
step four rolling
And (3) carrying out multi-pass rolling on the bar subjected to the aging heat treatment, wherein the deformation of each pass is between 10 and 30 percent, and finally obtaining the composite board with the thickness of 0.1 to 1 mm.
2. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board according to claim 1; the method is characterized in that; the as-cast Zn-Li-x ternary alloy is prepared by the following steps:
(1) Smelting: firstly, putting a high-purity Zn matrix into a smelting crucible, adding high-purity Li metal after Zn is melted, stirring for a period of time after adding to ensure that different components are uniformly distributed, adding a high-purity third element by the same method after stirring for continuous stirring when preparing a ternary alloy, and preheating equipment and raw materials to a certain degree in the smelting process, wherein the preheating is generally carried out at 200-300 ℃; when smelting, controlling the temperature to be 400-600 ℃;
(2) Casting: the heating device can be turned off after the mixture is uniformly stirred, impurities on the surface of the melt can be removed after the mixture is stable in temperature, the mixture is poured in a die, and the die is removed after the mixture is completely cooled and solidified, so that the cast alloy with the expected size can be obtained.
3. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: in the first step, the homogenizing annealing temperature is 295-305 ℃ and the homogenizing annealing time is 46-50 h.
4. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: and step two, taking out the zinc alloy cast ingot A immediately after heat preservation for 60min at 295-305 ℃ and carrying out hot extrusion in extrusion equipment through a die with fixed size to obtain a bar with the diameter of 15-17 mm.
5. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: in the fourth step, the bar after the time-effect heat treatment is rolled for multiple times, the deformation of each pass is between 10 and 30 percent, and the deformation of the first rolling is larger than the deformation of any subsequent rolling; the deformation of the nth rolling is larger than that of the n+1th rolling;
or (b)
In the fourth step, the bar after the time-effect heat treatment is rolled for multiple times, the deformation of each pass is between 10 and 30 percent, and the deformation of the first rolling is smaller than the deformation of any subsequent rolling; and the deformation amount of the nth rolling is smaller than that of the n+1th rolling.
6. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: when a Zn-Li-Mg as-cast alloy containing 0.5wt% Li and 0.1 wt% Mg is used,
homogenizing annealing at 300 deg.c for 48 hr, and water quenching at room temperature to obtain homogeneous Zn-0.5-0.1% Mg alloy ingot; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 30 percent, the rolling times are 5 times, the deformation of each time is decreased, and the deformation of the last time is 10 percent to obtain the Zn-0.5 percent Li-0.1 percent Mg composite plate; the hardness, modulus, tensile strength and elongation of the Zn-0.5 percent Li-0.1 percent Mg composite board are respectively 1.01GPa, 142.37GPa, 306.5MPa and 27.9 percent.
7. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: when a Zn-Li-Mg cast alloy containing 0.5wt% of Li and 0.1% of Mg is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Mg alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 10 percent, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 30 percent to obtain a Zn-0.5 percent Li-0.1 percent Mg composite plate; the hardness, modulus, bending strength and elongation of the Zn-0.5 percent Li-0.1 percent Mg composite board are respectively 0.98GPa, 136.43GPa, 318.6MPa and 26.8 percent.
8. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: when a Zn-Li-Ag cast alloy containing 0.5wt% of Li and 0.1% of Ag is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Ag alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is 30-10%, the deformation of the first time is 30%, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 10%, so as to obtain the Zn-0.5% Li-0.1% Ag composite plate; the hardness, young's modulus, bending strength and elongation of the Zn-0.5% Li-0.1% Ag composite plate are respectively 1.02GPa, 83.17GPa, 251.6MPa and 92.7%.
9. The method for synchronously improving the hardness, the strength and the elongation of the medical degradable Zn-Li-x ternary composite board is characterized by comprising the following steps of: when a Zn-Li-Ag cast alloy containing 0.5wt% of Li and 0.1% of Ag is adopted, the homogenizing annealing temperature is 300 ℃ and the homogenizing annealing time is 48 hours, and a Zn-0.5% Li-0.1% Ag alloy cast ingot with uniform structure is obtained by adopting room temperature water quenching; then taking out the obtained cast ingot immediately after heat preservation for 1h at 300 ℃ and performing hot extrusion in extrusion equipment through a die with fixed size to obtain a bar material, wherein the extrusion ratio in the process is about 10:1; then, carrying out artificial aging heat treatment on the extruded bar material at 200 ℃ for 1 h; finally, 5 times of rolling are carried out on the bar after the artificial aging heat treatment, the deformation of each time is between 30 and 10 percent, the deformation of the first time is 10 percent, the rolling times are 5 times, each time of increasing the deformation, and the deformation of the last time of rolling is 30 percent to obtain a Zn-0.5 percent Li-0.1 percent Ag composite plate; the hardness, young's modulus, bending strength and elongation of the Zn-0.5% Li-0.1% Ag composite plate are respectively 0.99GPa, 81.36GPa, 254.8MPa and 94.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310724956.5A CN116770133A (en) | 2023-06-19 | 2023-06-19 | Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310724956.5A CN116770133A (en) | 2023-06-19 | 2023-06-19 | Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116770133A true CN116770133A (en) | 2023-09-19 |
Family
ID=88009338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310724956.5A Pending CN116770133A (en) | 2023-06-19 | 2023-06-19 | Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116770133A (en) |
-
2023
- 2023-06-19 CN CN202310724956.5A patent/CN116770133A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101277297B1 (en) | High-strength high-ductility magnesium alloy extrusions with low anisotropy and manufacturing method thereof | |
| KR100994812B1 (en) | High-strength high-ductility magnesium alloy extrudate and manufacturing method thereof | |
| KR100993840B1 (en) | Magnesium alloy panel having high strength and manufacturing method thereof | |
| KR101303585B1 (en) | Magnesium alloy sheet having excellent room temperature formability and method of fabricating the same | |
| JP6607464B2 (en) | Formable magnesium-type wrought alloy | |
| JP5515167B2 (en) | Commercial magnesium alloy sheet with improved room temperature formability and method for producing the same | |
| CN1969051A (en) | Middle alloy for copper alloy casting and its casting method | |
| KR101078308B1 (en) | Magnesium alloy panel having high strength and manufacturing method for the same | |
| JP5233607B2 (en) | Aluminum alloy plate excellent in formability and method for producing the same | |
| CN111004950B (en) | 2000 aluminium alloy section bar and its manufacturing method | |
| US10947609B2 (en) | Magnesium alloy having excellent mechanical properties and corrosion resistance and method for manufacturing the same | |
| WO2013115593A1 (en) | Machining magnesium alloy capable of being heat treated at high temperature | |
| US20240263279A1 (en) | High strength microalloyed magnesium alloy | |
| KR101400140B1 (en) | Preparing method for magnesium alloy extrudate and the magnesium alloy extrudate thereby | |
| KR20160136832A (en) | High strength wrought magnesium alloys and method for manufacturing the same | |
| CN113388764A (en) | High-strength 7-series aluminum alloy for automobile anti-collision beam and automobile anti-collision beam | |
| CN115874093B (en) | 700 MPa-grade Al-Zn-Mg-Cu aluminum alloy extrusion material and preparation method thereof | |
| KR20190000756A (en) | Magnesium alloy sheet having high room temperature formability and high strength and method for fabrication | |
| CN116770133A (en) | Method for synchronously improving hardness, strength and elongation of medical degradable Zn-Li-x ternary composite board | |
| KR101252784B1 (en) | Magnesium alloy sheet having high strength and high formability and method for manufacturing the same | |
| JP3840400B2 (en) | Method for producing semi-melt molded billet of aluminum alloy for transportation equipment | |
| CN112342442A (en) | Method for manufacturing and preparing materials by using aluminum functional connecting piece and fastening piece | |
| JP4121266B2 (en) | Method for producing semi-molten billet of aluminum alloy for transportation equipment | |
| CN117821819B (en) | High-strength and high-toughness corrosion-resistant magnesium alloy and preparation method thereof | |
| CN109457157A (en) | A kind of magnesium alloy profiles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |